Low-temperature catalytic hydrogenation of bio-based furfural and relevant aldehydes using cesium carbonate and hydrosiloxane

Selective hydrogenation of unsaturated compounds is mainly carried out by using high-pressure hydrogen in the presence of a precious or transition metal catalyst. Here, we describe a benign approach to efficiently catalyze the hydrogenation of furfural (FUR) to furfuryl alcohol (FFA) over commercially available cesium carbonate using nontoxic and cheap polymethylhydrosiloxane (PMHS) as hydrogen source. Good to excellent FFA yields (≥90%) could be obtained at 25–80 °C by appropriate control of the catalyst dosage, reaction time, and the hydride amount. FUR-to-FFA hydrogenation was clarified to follow a pseudo-first order kinetics with low apparent activation energy of 20.6 kJ mol−1. Mechanistic insights manifested that PMHS was redistributed to H3SiMe, which acted as the active silane for the hydrogenation reactions. Importantly, this catalytic system was able to selectively reduce a wide range of aromatic aldehydes to the corresponding alcohols in good yields of 81–99% at 25–80 °C in 2–6 h.